Hydrolysis of halogenated hydrocarbons



Patented July 10, 19 34 nrnnorrsrs F nanocnna'riin nrnnocannons JohannA. Bertsch, St. Louis, 'Mo. ,-..-assisn0r, by.

No Drawing.

mesne assignments, r to ellum!!! =.Chemical Company, a corporation ofDelaware Application January :1 1931 Serial No. 512,154

9 Claims. (01. eta-151) This invention relates to thehydrolysis ofhalogenated hydrocarbon according to which the hydrocarbon, such aschlorbenzol is mixed with steam and caused to interact at elevatedtemperatures in the presence of a novel class of catalytic bodies forthis reaction.

It has been proposed heretofore to manufacture phenol from chlorbenzolby passing the vamm or chlorbenzol mixed with steam at elevated- 10temperature over various catalytic compositions.

Among these may be mentioned alumina, unglazed porcelain, silica gel, aswell as combinations oi silica gel, aluminum oxide or aluminum hydroxidewith promoters consisting of salts of various metals including copper,nickel, cobalt,

etc; According to the present invention, I proj vide a characteristicclass of compositions for the purpose of effecting the hydrolysis, whichnot only appears to function in a manner unlike the material recommendedheretofore, but also enables. one to obtain results which in mostin-'stan'ces are superior to those obtainable with known materials, and inaddition afiords certain lytic material may contain one or more pro-'-moter elements in chemical combination therewith of which the followingmay be mentioned: copper, silver, nickel, cobalt, gold and metals of theplatinum group. A large variety bf material may be included which haveno ill some instances indeed'have aldesirable eii'ect. Among these maybeincluded the alkali metals, as well as the alkaline earth metals. Thepresence of iron appears to havea deleterious .eifect. One convenientmethod of preparing a catalyst consists in exchangingordinary permutitewith a compound of the promoter elements hereinabove mentioned. Theresulting product is a 'zeolite in which the promoter element is in'exchangeable form. The method of preparing" the catalyst may follow byanalogy the procedure described in Patent No. 1,256,032, wherein azeolite, such as sodium permutite is treated with nickel nitrate wherebythe sodium is replaced by the nickel or as described in U. S. Patent No.1,215,396 wherein sodium zeolite is treated with a dilute,

,55 acidified solution of palladium subchloride. It

technical advantagesnot aiiorded by the present effect, and in desired,however, the promoter element may be essentially in the nonexchangeableform. For this purpose, one may advantageously proceed in thepreparation oi the catalyst substantially as'. described in my jointPatent No. 1,782,353. The compounds .formed according to the presentinventlon maybe impregnated in a carrier substance while in a gelatinousor liquid form and thereafter molded into pellets of a desired size.Thus following the procedure described in my co-pending jointapplicatiom'S N. 95,771, filed March 18-, 1926.

The followingexamples of the manufactureof the catalysts arespecifically set forth,-it being understood that these are illustrativeonly and that for furtherexam'ples for the preparation of a catalystreference may be had to the literature now available in the art,notably, my Joint patent and application.

'It is to be noted that I make no claim in this applicationto the methodof manufacturing the catalyticmass nor to the resulting product, but'Ido claim broadly the use in the hydrolysis of chlorinated hydrocarbonsof silicious or non-silicious artificial base exchange bodies, eitheralone or when; mixed with fillers such as kieselguhr, tripoli, opalite,carrara silica, .pumice stone, aluminum' ,oxide, and various othermaterials upon which the active catalytic mass may be deposited, or withwhich it may be molded into pellets.

. It is to be-further understood that the catalytic mass may andprobably does undergo physical and chemical changes in the course of itsuse. In

many instances, these changes do not have a deleterious. effect upontheqquality oi the catalyst.

Accordingly, ,it is to be understood that the claim comprehe'nds the usein the aforementioned reaction not only the freshly prepared catalyst,but the products resulting after use in promoting the desired catalyticreaction; Anexample of'what is meant may be illustrated by referring tothe hydrolysis of chlorbenzol with steam in the presence of a coppersilica catalyst (madeaccording to Example 1); .The original material isa characteristic permutite-in that it has strong base exchange.properties. In the course of the use of the material a change inchemical structure takes place, thecopper Tpresent being reduced atleast in part to metallic copper. as can beseen from the appearance oithe used mass which resembles f-reshlyrejduced metalicwcopper metal.Nevertheless, the product retains its activity and may be 'usedindeflnitely :E,In-,th.is--connection, it is interesting to .note.; that:when silica gel, '"which has 1,

' suspension of hydrated lime or carbonate of "lime' been impregnatedwith a copper salt, is employed,

the activity of the mass diminishes, the copper salt appears .to changeinto the form of a black oxide and does not reduce to metallic coppereven after prolonged use. Silica gel is further distinguishable 'frompermutite or base exchange bodies in that the former as offered on themarket possesses marked gas absorption properties whereas the latter aresubstantially without gas absorptive power. The following specificexamples illustrate various embodiments of the principles of myinvention.

Example 1 .-A copper complex .catalyst is made by first preparing andthereafter mixing two solutions: (1) containing 620 parts of sodiumwaterglass (20.95% $102) which has been mixed with 3000 parts of water,180 parts of 2 normal sodium which may if desiredbe washed again. Afterdrying, the fragments are charged in a 2 inch externally heatednon-ferrous tube and optionally exposed to a stream of air containing asmall amount of HCl gas while raising thetemperature up to 425 C.Thereafter and preferably while maintaining a temperature of 325-450 C.a mixture of chlorbenzene and steam is conducted over the catalytic massresulting in the hydrolysis of the chlorbenzene to phenol. The vaporscontain-- ing' unreacted chlorbenzene and steam together with phenol andhydrogen chloride are treated to separate the unreacted chlorbenzeneafter the admixture of steam is conducted again over a catalyst therebypermitting of a cycle process. In the event the hydrogen chloride is notrequired as such, the vapors may be conducted through a therebyabsorbing the H01 and otherwise simplifying the separation of theunreacted gas mixture. I

The above complex sodium copper silicate has strong base exchange power,it being capable of removing by a reversible process 2500 grains ofhardness from'water per cubic foot of the catalyst mass. If the abovecomplex is treated with a.

5% copper nitrate solution, part of the alkali is.

exchanged for the copper. The resulting mass is equally satisfactory forthe hydrolysis processes which are the subject of the .presentinvention. In an analogous manner the alkali may be exchanged forsilver, using a 5% silver nitrate'solution. The resulting product isdried and may be employed to advantage in the hydrolysis of halogenatedhydrocarbons. It should be understood that in the aforementioned exampleas. well as those hereinafter set forth, the' copper content (meaninghere the promoter metal content) as well as the silica content may bemodifiedand varied within wide limits without impairing substantiallythe efficacy of the resulting mass. Thus, for example, conversions of95% of chlorbenzene to phenol have been obtained .with theaforementioned zeolitic catalyst, not-' withstanding the fact that theproportions of After the solutions are amount of potassium zeolite.

copper and silver as well as silica were varied in the individual tests.

Example 2.In lieu of monochlorbenzene em- I changed for copper, thematerial is dried first at a temperature preferably below 100 C. Theamount of copper so introduced is largely optional. A product wherein asmuch as 20% of the sodium is exchanged for copper has been found to givesatisfactory results.

The resulting dried product is deposited in a catalytic chamber,preferably of a non-ferrous composition through which a mixture of steamand chlorbenzol is passed at atemperature of T 325 425 C. .A yield ofphenol from chlorbenzol of over 90% is easily obtained.

Example 4.-The washed copper zeolite prepared as described above andbefore desiccation is mixed. with a pulverant carrier, suchaskieselguhr, silica, asbestosfibers, etc. Thereafter the material isformed into pellets of suitable size and dried. The product is employedin a manner analogous to that described inExample 1'.

Example 5.In Example 1, substitute for the i In this case, the silver isexchanged for the sofound to function as a. hydrolysis catalyst althoughthe temperature required for the reaction will in general be found to beslightly higherthan, in the case of copper zeolites. The material may bemixed with a carrier substance or used in an unaltered form. ,I

Example 6.--An excellent catalyst may be prepared by employing a mixtureof copper and silver sulphates which are exchanged for the sodium in anartificial sodium zeolite, such as is described in Example}. Example '7.In lieu of the sodium zeolite specifled in Example 1, substitute anequivalent In other respects proceed as described in the previousexamples.

The resulting product will be found to be equally satisfactory in thehydrolysis of chlorinated aromatic compounds.

Example 8.--A non-silicious permutite may be prepared;advantageously bymixinglo parts'of aluminum oxide in the form of potassium aluminate,dissolved in water to which there is added an ammonium solutioncontaining one part of -'copper sulphate.

Add a solution of aluminum sulphate, care being exercised to insurethorough agitation during the addition. After an amount of aluminumsulphate has been added which is substantially the mol equivalent of thepotassium aluminate' present, the mixture is applied either before orafter washing to remove soluble salts, to afragment carrier after whichit is employed as in the previous examples. v The soluble salts areseparated by decanting the clear solution and thereafter washing the gelwhich has been formed by the addition of the aluminum sulphate,repeatedly with water.

Example 9.-'-A mixed silver copper aluminum I catalyst may be preparedby causing a mixture of copper sulphate a,l0% solution of silversulphate.

'110- dium.- The resulting product will likewise be potassium aluminatecontaining copper ammo-' nium sulphate to react with a solution ofaluminum sulphate containing silver sulphate.

It is to be understood that the procedure observed in the catalysis ofchlorinated compositions is the same in all of the aforementionedexamples,

- although modifications m the temperature and the proportions-of steamand chlorbenzol will be found advisable under any specific plantoperation conditions. Similarly, other halogenated hydrocarbons maybesubstituted both of aromatic and aliphatic specie. Other combinations ofthe metals previously enumerated as having a promotive action in thiscatalytic reaction may be prepared following in general the proceduredescribed,in the patents and applications previously enumerated.Similarly, oxides of titanium, chromium, boron, tin, etc., may besubstituted for the silica and alumina described in detail hereinaboveand by references to the patents and application.

It will thus appear that the invention is susceptible to numcrablemodifications and variations without departing from the'broad concept,

5 to wit, complex artificial product having base exchange properties ascatalyst in the hydrolysis of halogenated hydrocarbons. p v

WhatIclaim is: I

1. The method of preparing phenols which .10 comprises reacting anuclear halogenated benzene series hydrocarbon with steam in thepresence of an artificial inorganic base exchange body containing as acomponent an element which. is a clear halogenated benzenehydrocarbon-to react promotor for the hydrolysis of the hydrocarbon to aphenol.

2. The method as defined in claim 1 in which the promotor element iscopper.

.3. The method as defined in claim 1 and further characterized in thatthe halogenated hydrocarbon is monochlorbenzene.

4. The method which comprises causing a nu-' clear halogenated benzenehydrocarbon to react with steam in the presence of an artificial baseexchange body containing silica in combination and containing as anadditional component a I metal which is a catalyst for hydrolysis by'the steam.

5. The method which comprises causing a nuwith steam in the presenceoi apermutite containing as a component a metal which is, a promoter ofhydrolysis by steam.

6. The method as defined in claim 5 and turther characterized in thatthe permutite contains silica in chemical combination.

7. The method as defined in claim 5 and fur-.' ther characterized inthat the permutite contains silica and copper in chemical combination.

8. The method-as defined in claim 5 and Iurther characterized in thatthe permutite contains silver in chemical combination.

9. The method as defined in claim 5 and fur I ther characterized in thatthe permutite contains both silver andcopper in chemical combinatidi.

" JOHANN A. BERTSCH.

July 10, 1934.

certified that error appears in the printed specification of the LettersPatent should be read with CERTIFICATEYOF CORRECTION.

more no; 1.966. 281. I

JOHANN A. BERTSCH.

It is hereby 5 above numbered pater-i requiring correction as follows:Page 2, line 42, after.

"-cl lorbenzene" insert which; and tl at the said this correctiontherein that the same may conform to the'record of 'the case in thePatent Office.

Signed and sealed this lltli day .of September, A. D. 1934.

v. tflit Frazer r30 "5"? emission! 9 Patents, 7

. potassium aluminate containing copper ammo-' nium sulphate to reactwith a solution of aluminum sulphate containing silver sulphate.

It is to be understood that the procedure observed in the catalysis ofchlorinated compositions is the same in all of the aforementionedexamples,

- although modifications m the temperature and the proportions-of steamand chlorbenzol will be found advisable under any specific plantoperation conditions. Similarly, other halogenated hydrocarbons maybesubstituted both of aromatic and aliphatic specie. Other combinations ofthe metals previously enumerated as having a promotive action in thiscatalytic reaction may be prepared following in general the proceduredescribed,in the patents and applications previously enumerated.Similarly, oxides of titanium, chromium, boron, tin, etc., may besubstituted for the silica and alumina described in detail hereinaboveand by references to the patents and application.

It will thus appear that the invention is susceptible to numcrablemodifications and variations without departing from the'broad concept,

5 to wit, complex artificial product having base exchange properties ascatalyst in the hydrolysis of halogenated hydrocarbons. p v

WhatIclaim is: I

1. The method of preparing phenols which .10 comprises reacting anuclear halogenated benzene series hydrocarbon with steam in thepresence of an artificial inorganic base exchange body containing as acomponent an element which. is a clear halogenated benzenehydrocarbon-to react promotor for the hydrolysis of the hydrocarbon to aphenol.

2. The method as defined in claim 1 in which the promotor element iscopper.

.3. The method as defined in claim 1 and further characterized in thatthe halogenated hydrocarbon is monochlorbenzene.

4. The method which comprises causing a nu-' clear halogenated benzenehydrocarbon to react with steam in the presence of an artificial baseexchange body containing silica in combination and containing as anadditional component a I metal which is a catalyst for hydrolysis by'the steam.

5. The method which comprises causing a nuwith steam in the presenceoi apermutite containing as a component a metal which is, a promoter ofhydrolysis by steam.

6. The method as defined in claim 5 and turther characterized in thatthe permutite contains silica in chemical combination.

7. The method as defined in claim 5 and fur-.' ther characterized inthat the permutite contains silica and copper in chemical combination.

8. The method-as defined in claim 5 and Iurther characterized in thatthe permutite contains silver in chemical combination.

9. The method as defined in claim 5 and fur I ther characterized in thatthe permutite contains both silver andcopper in chemical combinatidi.

" JOHANN A. BERTSCH.

July 10, 1934.

certified that error appears in the printed specification of the LettersPatent should be read with CERTIFICATEYOF CORRECTION.

more no; 1.966. 281. I

JOHANN A. BERTSCH.

It is hereby 5 above numbered pater-i requiring correction as follows:Page 2, line 42, after.

"-cl lorbenzene" insert which; and tl at the said this correctiontherein that the same may conform to the'record of 'the case in thePatent Office.

Signed and sealed this lltli day .of September, A. D. 1934.

v. tflit Frazer r30 "5"? emission! 9 Patents, 7

